Silicon containing .alpha.-cyanoacrylate monomers are known.
Buck, U.S. Pat. No. 4,012,402, discloses bis-(alkyl cyanoacrylate) substituted diorganosiloxanes, prepared by a cumbersome Dieis-Alder/reverse Dieis-Alder reaction procedure which is not practical for large quantity commercial synthesis.
Kadykov, et. al., Plast. massy, 1984, No. 10, pp 8-9, alleges that diacryl-.alpha.-cyano-.beta.-hydroxypropyldimethylsiloxane was synthesized by reaction of cyanoacrylic acid and diepoxydimethylsiloxane in the presence of tertiary amine catalyst.
Diechert, U.S. Pat. No. 4,153,641, states that diorganosiloxane acrylic monomers, including siloxane cyanoacrylic monomers of the general type disclosed in U.S. Pat. No. 4,012,402, may be used in the preparation of acrylic contact lens formulations but does not illustrate synthesis or use of any such siloxane cyanoacrylates.
Monocyanoacrylate ester compounds having silicon substitution are disclosed in Mikuni, et. al., U.S. Pat. No. 5,140,084.
2-Cyano-2,4-pentadienoate esters are well-known monomers that cure by an anionic mechanism and have activity similar to cyanoacrylate esters. The prior art contains references to homopolymerization and polymerization in mixture with cyanoacrylates and other monomers.
Birch, et. al., J. Chem. Soc., 1923, 2448, discloses the reaction of diethyl ketone and ethyl cyanoacetate, catalyzed by zinc chloride.
Gerber, U.S. Pat. No. 3,316,227 (1967); and Polym. Prepr. Amer. Chem. Soc., Div. Polym. Chem., 1968,9(1), 434-41, discloses the reaction of acrolein and ethyl cyanoacetate, catalyzed by zinc chloride in dioxane solvent.
Rao, et. al., Tetrahedron Lett., 1991, 32(41), 5821-5822, discloses the reaction of aromatic aldehydes and ethyl cyanoacetate, catalyzed by zinc chloride.
Trofimov, et. al., GB 1,415,102 (1975), discloses formulations of cyanoacrylates and cyanopentadienoates exhibiting improved thermal stability.
Quinn, et. al., U.S. Pat. No. 3,554,990, discloses synthesis of cyanopentadienoates and formulations with cyanoacrylates exhibiting improved shear strength.
Teramoto, et. al., U.S. Pat. No. 4,313,865, discloses synthesis of cyanopentadienoates and formulations with cyanoacrylates exhibiting improved impact resistance, peel resistance, heat resistance, and water resistance.
Millet, U.S. Pat. No. 4,425,471, discloses synthesis of cyanopentadienoates and formulations of same with cyanoacrylates exhibiting improved impact and peel strengths.
Yeh, U.S. Pat. No. 5,136,065 discloses propargyl esters of 2-cyano-4-aryl-2,4-pentadienoic acids and the hydrosilation thereof with an organohydrogensilane or organohydrogensiloxane to produce organosilanes and organosiloxanes substituted with 2-cyano-5-aryl-2,4-pentadienoate ester groups. However the 5-aryl group interferes with anionic polymerization so these monomers are not suitable as additives to, or substitutes for, cyanoacrylates. Furthermore, hydrosilation of a propargyl cyanopentadienoate which is not substituted in the 5 position is not a suitable synthetic route for cyanopentadienoate esters because of the much greater reactivity of the 5-unsubstituted cyanopentadienoate group.
In copending U.S. patent application Ser. No. 07/769,511, filed Oct. 1, 1991, incorporated herein by reference, there are described monofunctional silane and siloxane cyanoacrylate and cyanopentadienoate compounds.